Hefei National Lab for Physical Science at Microscale and Department of Modern Physics, University of Science and Technology of China, Hefei 230026, China.
J Chem Phys. 2012 Mar 7;136(9):094306. doi: 10.1063/1.3691103.
The extensive study of outer- and inner-valence satellites of carbon dioxide by electron momentum spectroscopy is reported. The experiments have been performed using a high-sensitivity electron momentum spectrometer employing non-coplanar symmetric geometry at impact energy of about 1200 eV. Binding energy spectrum up to 50 eV, above the first double ionization threshold (~37.3 eV), is presented. Four main peaks and twelve satellites have been identified including four embedded in the double ionization continuum, among which the two beyond 42 eV are observed for the first time. High accuracy symmetry-adapted-cluster configuration interaction general-R calculation with aug-cc-pVTZ basis sets has also been performed and the result is in line with the experimental ionization spectrum except the relative intensities for some of the satellites in inner-valence region. The experimental momentum profiles for both the main ionization transitions and satellites have been obtained and compared with theoretical calculations by HF and B3LYP methods with 6-311++G∗ and aug-cc-pVTZ basis sets. Through comparison, the detailed assignments of the satellite bands have been achieved and the pole strengths for the relevant shake-up transitions are determined experimentally for the first time.
本文报道了利用非共面对称几何结构的高灵敏度电子动量谱仪对外层和内层二氧化碳价层卫星进行的广泛研究。实验在约 1200eV 的冲击能下进行。给出了高于第一次双电离阈值（约 37.3eV）、高达 50eV 的结合能谱。已确定了四个主要峰和十二个卫星，其中四个嵌入在双电离连续体中，其中两个超过 42eV 的是首次观察到的。还进行了高精度的对称自适应簇组态相互作用全原子极化基组（aug-cc-pVTZ）计算，结果与实验电离光谱一致，除了内层价区一些卫星的相对强度。还获得了主电离跃迁和卫星的实验动量分布，并通过 HF 和 B3LYP 方法与 6-311++G∗和 aug-cc-pVTZ 基组进行了理论计算。通过比较，首次实现了卫星带的详细分配，并实验确定了相关激发跃迁的极强度。
